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International Journal of Recent Scientific Research Vol. 4, Issue, 6, pp.1005 1010, July, 2013 ISSN: 0976-3031
ARTICLE INFO
Article History:
Received 14th, June, 2013 Received in revised form 26th, June, 2013 Accepted 16th, July, 2013 Published online 30th July, 2013
Key words: Jatropha, Ethyl ester, esterification, transesterification, Biodiesel, biodiesel plant
INTRODUCTION
Biodiesel is renewable in nature and can be blended at any level with petroleum diesel to create a biodiesel blend or can also be used in its pure form. Just like petroleum derived diesel (petro-diesel), biodiesel operates in compression ignition (CI) engine; which essentially requires very little or no engine modifications, because quite similar properties. Technical advantages of biodiesel include biodegradability, excellent lubricity and high flash point, which make the fuel safe to handle and transport (Knothe, 2002). Besides biodegradable, it is nontoxic and has low emission profiles making it environmentally beneficial (Michael et al, 1998). Both edible oils such as Soybean, Rapeseeds, Canola, Sunflower, Cottonseeds, etc. and non-edible oils like Jatropha (Jatropha curcas), Karanja (Pongamia pinnata), Jojoba (Simmondsia chinensis), Mahua (Madhuca latifolia) etc. have been tried to supplement diesel fuel in various countries. In US, biodiesel program is based on their surplus edible oils like soybean and in Europe from rapeseed and sunflower oils. However in India emphasis has always been on exploring the possibility of using non-edible oils for biodiesel production and a program has been undertaken for large-scale cultivation of jatropha on wastelands thoughout the country (Planning Commission Report, 2003). There are a number of ways to make the vegetable oil equivalent to diesel fuel. These methods include; Transesterification, Pyrolysis, Micro
* Corresponding author: K Kundu TERI University, New Delhi; 2MERADO, Ludhiana
Emulsion, blending and thermal depolymerization (Srivastava and Prasad, 2000). The most common method to prepare biodiesel is transesterification of vegetable oil with a monohydric alcohol (Figure 1) or esterification of fatty acids (Figure 2). Transesterification is one of the reactions that are used to prepare esters (Otera, 1993). This is not a new process and by all accounts it was conducted as early as 1853, by the two chemists E. Duffy and J. Partrick. One of the first uses of transestrified vegetable oil was powering heavy-duty vehicles isSouthAfricabeforeWorldWar II(www.dfwbiodiesel.com/tech nology.html). Transesterification of vegetable oil is the process of reacting triglycerides with methanol in order to obtain fatty acid methyl esters and glycerol and the process is important for preparation
R 1COO R2 COO R 3COO CH2 CH CH2 Alcohol + 3ROH Catalyst R 1COOR R 2COOR R 3COOR Alkyl esters + HO CH2 HO CH HO CH2 Glycerol
Triglyceride
Catalyst R1COOH + ROH Fatty acid Alcohol Acid R1COOR Alkyl esters + H2O
International Journal of Recent Scientific Research, Vol. 4, Issue, 7, pp. 1005 - 1010, July, 2013 Alkali catalysts are commonly used for transesterification of oils since they require short reaction time even at room temperature (Encinar et al., 2002). Other types of catalysts used for transesterification includes bronsted acids (sulfuric acid, sulfonic acid, etc.) (Goff et al., 2004), heterogeneous catalysts such as basic zeolites, alkaline metal compounds, enzymes such as lipases (Meher et al., 2006) and also anion exchange resins (Toda et al., 2004). The high free fatty acid (FFA) content oil needs acid catalyzed pretreatment to lower the acid value by esterification of FFA (Figure 2), followed by alkali catalyzed transesterification of the glycerides for preparation of fatty acid alkyl esters (Canakci and Gerpen, 1999; Canakci and Gerpen, 2001). The transesterification of vegetable oil is also accomplished in supercritical methanol without catalyst. Saka and Kusdiana (2001) had studied the preparation of biodiesel in supercritical methanol at temperature > 239.4C and pressure > 8.09MPa where the reaction was completed in 4minutes. In addition, the process has been used for simultaneous esterification of free fatty acids and transesterification of triglyceride for biodiesel preparation from high free fatty acid rapeseed oil (Kusdiana and Saka, 2001; Warabi et al., 2003). Non-catalytic alcoholysis of oils for biodiesel preparation has also been reported in the literature (Dasari et al., 2003; Yamazaki et al., 2004). Ethanolysis is often discussed as the more environmentally friendly alternatives, as it allows the production of an entirely natural fuel, if the alcohol is derived from fermentation of harvested residue, i.e. bio-ethanol. As opposed to this, methanol is mainly produced from fossil sources. A very few reports are available for transesterification of vegetable oil with higher grade of alcohol and these reports reveal that the reaction is difficult at selected temperature and more problems on separation of glycerol and biodiesel phase. Most of the researches on esterification of jatropha oil have been done with methanol, being cheaper. A very few studies have been done with ethanol despites its distinct advantages over methanol. Ethanol is renewable in nature and it is preferable to prepare biodiesel, a renewable fuel with the use of all renewable ingredients. Thus, here an attempt has been made to optimize process variables for the ethanolysis of jatropha oil. biodiesel production have been optimized by carrying out the factorial design of experiment. The responses have been measured by yields of ester and the viscosity of vegetable oil. As per the literature review and past experience of the various researchers, the experimental process variables can be classified as follows: Quantitative variables Molar ratio of vegetable oil and alcohol Reaction temperature Reaction time Amount of catalyst (% wt of vegetable oil) Settling time Rate of agitation (Mixing intensity, rpm) Qualitative variables Vegetable oil Alcohol Purity of Alcohol In this experimental plan, both quantitative and qualitative variables have been analyzed for maximum biodiesel yield. Out of above explained variables (Qualitative and Quantitative variables) the following parameters were kept constant during the experiments: Molar ratio of vegetable oil and alcohol (6:1) Settling time (12 hrs) Rate of agitation (500 rpm)
Stirrer
Thermocouple Condenser
Water bath
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International Journal of Recent Scientific Research, Vol. 4, Issue, 7, pp. 1005 - 1010, July, 2013 Table 1 Physico-chemical properties of jatropha oil
Property Free fatty acid Acid value Saponification value Unsaponifiable matter Iodine value Water content Unit % mg KOH/g mg KOH/g w/w percent g I2/100g ppm Jatropha oil 0.46 0.94 179 3.2 94 667
jatropha ethyl ester was increases and clear separation of layer was observed at some level of catalyst. The highest yield of JEE was found with 85% aqueous ethanol with 3.0% catalyst concentration. Thus this experimental optimization investigation concluded that, the ethyl ester production required some degree of aqueous ethanol.
Influence of reaction time and temperature on the yield and viscosity of JEE
Keeping purity of ethanol constant 85%, reaction time and temperature were varied with different process chain like JEE9, JEE10, JEE11 and JEE12. The temperature was varied from 60 to 40C (at 5C slab) variation and reaction time was varied from 75 to 30 minutes (at 15 minute slab). Accordingly, the yield and viscosity were measured. It was found that the JEE yield varied from 66.1% to 45.9% for JEE9. It was also clearly observed that maximum yield of 66.1% was observed with 60C reaction temperature and 75 minute reaction time. The correspondence viscosity was observed to be 5.4 cSt. It was observed that, for all process chains, at lower temperature regime of 40C and 45C, no ester yield was observed. At 50C with reaction time of 60, 45 and 30 minutes, the viscosity of JEE was not in the range of standard limits and also the lower yield of ester was observed. However, again with 2% catalyst concentration (JEE10), it was found that maximum yield 68.4% was observed with 60C and 55C reaction temperature and 60 minutes reaction time and correspondence viscosity was 5.4 and 6.1 cSt. It is clearly seen from the Figure 4 that approximately similar yields of ester were observed for the process JEE9 and JEE10 at different catalyst concentrations. At catalyst concentration of 2.5% (JEE11), the maximum yield of ester was found 74% at 75 minute reaction time and 55C reaction temperature. It is clearly seen that the yield of JEE was increased by 10% with catalyst concentration of 2.5% compare to catalyst concentrations of 1.5% and 2.0%. However, the corresponding viscosity values were not in an acceptable range.
Generally, it is recommended that vegetable should have FFA level below 1% and water content as low as possible but not exceeding 0.5% the fatty acid profile of jatropha oil are presented in Table 2. Table 2 Fatty acid composition Jatropha oil
Fatty acid (%w/w) Palmitic acid (C16:0) Stearic acid (C18:0) Oleic acid (C18:1) Linoleic acid (C18:2) Jatropha oil 13.6 6.2 47.2 31.0
Table 3 Effect of catalyst concentration on transesterification of jatropha oil with anhydrous ethanol
Process Chain JEE 1 JEE 2 JEE 3 JEE 4 JEE 5 JEE 6 Purity of Alcohol (%) 100 100 100 100 100 100 Catalyst Concentration (% wt of oil) 0.5 1.0 1.5 2.0 2.5 3.0 Reaction Time (min) 60 60 60 60 60 60 Reaction Temp (deg C) 60 60 60 60 60 60 Biodiesel Yield (% wt of oil) NS NS NS NS NS NS
By keeping aqueous ethanol (85%) constant and catalyst concentration was varied from 0.5 to 3.0% (at 0.5% slab). The observed results are summarized in Table 4. There were no separation found with catalyst concentration level upto 1.0% after that it was clearly observed that, the yield of JEE was increasing with increased catalyst amount and the highest yield of 76.8% was observed at 3.0% catalyst concentration. Further the experiment was set with different aqueous ethanol. For these sets of experiments, the catalyst concentration was kept constant at a previously optimized level 3.0% and the purity of ethanol was varied from 97.5% to 85% (at 2.5% slab) and the observed results are summarized in Table 5. It was observed that, as the aqueousness of ethanol was reduced, the yield of
Maximum yield of jatropha ethyl ester was found at 60C with 75 minute reaction time irrespective of catalyst concentration for JEE12 and corresponding viscosity 7.8 cSt, (Figure 5) which was in the acceptable range. It was thus concluded that, as the catalyst concentration increased the yield of jatropha ethyl ester (JEE) also increases with aqueous ethanol. Also, it can be concluded that production of jatropha ethyl ester is a good choice as it reduces the input cost of raw material resulting in reduced production cost of biodiesel apart the fact that use of bio-ethanol makes it completely renewable fuel. In order to further maximize the yield of JEE further experiments were conducted with this by varying other process parameters.
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International Journal of Recent Scientific Research, Vol. 4, Issue, 7, pp. 1005 - 1010, July, 2013 Optimization of quantitative variables for jatropha ethyl ester (JEE) order to further maximize the yield of JEE further experiments were conducted with this by varying other process parameters.
60
30
Influence of reaction time and temperature with variation in aqueousness of ethanol on the yield and viscosity of JEE In order to evaluate the effect of purity of ethanol on the yield and viscosity of jatropha ethyl ester (JEE), other important process parameters viz. reaction temperature and reaction time was varied with process chain JEE16, JEE17 and JEE18.
Table 4 Effect of catalyst concentration on transesterification of jatropha oil with aqueous ethanol
Process Chain JEE 7 JEE 8 JEE 9 JEE 10 JEE 11 JEE 12 Purity of Alcohol (%) 85 85 85 85 85 85 Catalyst Concentration (% wt of oil)) 0.5 1.0 1.5 2.0 2.5 3.0 Reaction Time (min) 60 60 60 60 60 60 Reaction Temp (deg C) 60 60 60 60 60 60 Biodiesel Yield (% wt of oil) NS NS 58.2 68.4 72.1 76.8
It is clearly seen from the Figure 4 that approximately similar yields of ester were observed for the process JEE9 and JEE10 at different catalyst concentrations. At catalyst concentration of 2.5% (JEE11), the maximum yield of ester was found 74% at 75 minute reaction time and 55C reaction temperature. It is clearly seen that the yield of JEE was increased by 10% with catalyst concentration of 2.5% compare to catalyst concentrations of 1.5% and 2.0%. However, the corresponding viscosity values were not in an acceptable range.
Five levels of reaction temperatures (60, 55, 50, 45 and 40C) and four levels of reaction time (75, 60, 45 and 30 minutes) was selected as a asymmetric factorial experiments. The obtained results are summarized in Figure 6 and Figure 7. It was observed that, for all process chains, at lower temperature regime of 45C and 40C, no ester formation was found. With varying temperatures from 60C to 50C the JEE yield varied from 32.4% to 68.2% for the process chain JEE16 and the
Maximum yield of jatropha ethyl ester was found at 60C with 75 minute reaction time irrespective of catalyst concentration for JEE12 and corresponding viscosity 7.8 cSt, (Figure 5) which was in the acceptable range. It was thus concluded that, as the catalyst concentration increased the yield of jatropha ethyl ester (JEE) also increases with aqueous ethanol. Also, it can be concluded that production of jatropha ethyl ester is a good choice as it reduces the input cost of raw material resulting in reduced production cost of biodiesel apart the fact that use of bio-ethanol makes it completely renewable fuel. In
highest yield (68.2%) was observed at 60C with 60 minute reaction time. However, the corresponding viscosity was 6.9 cSt. The viscosity ranged from 6.9 cSt to 9.2 cSt for the process chain JEE16 with variation of temperatures from 60C to 50C (with 5C slab) and reaction time of 75 minutes to 30 minutes (with 15 minutes slab). The results found were symmetric but the yield was lower compared to other process chains for JEE. For the process chain JEE17, the highest yield of ester was found at 60C with 75 minute reaction time and corresponding viscosity was observed at 7.6 cSt, which is not
1008
Re ac tio n
Ti m
e( mi n)
International Journal of Recent Scientific Research, Vol. 4, Issue, 7, pp. 1005 - 1010, July, 2013 The highest yield (82.3%) of process chain JEE18 was approximately 20% higher than compared to process chain JEE16 and JEE17. It is seen that in respect of viscosity and yield of ester, the results are very much symmetrical for the all the process chains. It has also been seen that with increasing the aqueousness of ethanol the yield of jatropha ethyl ester was also increasing. Thus the recommended process parameters for the production of jatropha ethyl ester (JEE) can be summarized as reaction time of 75 minute, reaction temperature of 60C, molar ration of 6:1, and catalyst concentration of 3.0% with 85% ethanol purity. The observed results also indicate that, for higher aqueousness ethanol, the biodiesel quality is very good compare to lower aqueousness of ethanol.
10 9 8
Viscosity (cSt)
7 6 5 4 360 55 45 30
Re ac t io nT im e( mi n)
Reac tio
n Te mper tu
50
60
CONCLUSIONS
No ester separation was found by using 100% ethanol at different level of catalyst concentrations from 0.5 to 3.0% and similarly at lower temperature regimes of 45C and 40C. With varying temperatures from 60C to 50C the yield was varied from 32.4% to 68.2%. For the process chain JEE17, the highest yield of ester was found at 60C with 75 minute reaction time and corresponding viscosity was observed 7.6 cSt, which is not in acceptable range. But, for process chain JEE18, the highest yield 82.3% was found with 75 minute reaction time at 60C and corresponding viscosity 5.3 cSt, which is lower than process chain JEE16 and JEE17. The highest yield (82.3%) of process chain JEE18 was approximately 20% higher than compare to process chain JEE16 and JEE17. It is seen that in respect of viscosity and yield of ester, the results are very much symmetrical for the all the process chains. It is also observed that with increasing the purity of ethanol the yield of jatropha ethyl ester was also increasing. The recommended process parameters for the production of jatropha ethyl ester (JEE) are: reaction time 75 minute, reaction temperature 60C, molar ration 6:1, and catalyst concentration 3.0% with ethanol purity 85%. The observed results also indicate that, for higher degree of proof of ethanol, the biodiesel quality is very good compare to lower proof of ethanol.
r e (d eg C
45
40
75
In the acceptable range. But, for process chain JEE18, the highest yield of 82.3% was found with 75 minute reaction time at 60C and corresponding viscosity observed was 5.3 cSt, which is lower than process chain JEE16 and JEE17.
100 90 80
) Biodiesel Yield (%
70 60 50 40 3060 45 30
Reac tion
Tem pertu re ( d
50
45
eg C )
40
75
Re ac tio nT im
60
55
e(
mi n
References
Canakci, M. and Van Gerpen, J. 1999. Biodiesel production via acid catalyst. Transactions of the ASAE, 42 (5) : 1203-1210. Canakci, M., Gerpen, J.V., 2001. Biodiesel production from oils and fats with high free fatty acids. Trans. ASAE 44 (6), 14291436. Dasari, M.A., Goff, M.J., Suppes, G.J., 2003. Non-catalytic alcoholysis kinetics of soybean oil. J. Am Oil Chem. Soc. 80 (2), 189-192 Encinar, J.M., Gonzalez, J.F., Rodriguez, J.J., Tajedor, A., 2002. Biodiesel fuel from vegetable oils: Transesterification of Cynara cardunculuc L. oil with ethanol. Energy Fuel 16 (3), 443-450. Goff, M.J., Bauer, N.S., Lopes, S., Sutterlin, W.R., Suppes, G.J., 2004. Acid catalyzed alcoholysis of soybean oil. J. Am. Oil Chem. Soc. 81 (1), 415-420. Knothe, G., 2002b. Structure indices in FA chemistry. How relavent is the iodine value? J. Am. Oil Chem. Soc. 79 (9), 847-854. Kusdiana, D., Saka, S., 2001. Methyl esterification of free fatty acids of rapeseed oil as treated in supercritical methanol. J. Chem. Eng. Japan 34 (3), 383-387.
Figure 6 Effect of reaction time and temperature on the yield of JEE with variation in purity of ethanol
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Viscosity (cSt)
7 6 5 4 360 55 45 30
60
40
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Figure 7 Effect of reaction time and temperature on the viscosity of JEE with variation of catalyst concentration and aqueous ethanol
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International Journal of Recent Scientific Research, Vol. 4, Issue, 7, pp. 1005 - 1010, July, 2013 Meher, L. C.; Naik, S. N. and Das, L. M.2004. Methanolysis of Pongamia pinnata (Karanja) oil for production of biodiesel. Journal Scientific and Industrial Research, 63, 913-929. Michael S. G. and Robert, L.M., 1998. Combustion of fat and vegetable oil derived fuels in diesel engines. Prog. Energy combust. Sci., Vol,24, pp125-164. Otera, J., 1993. Transesterification. Chem. Rev. 93 (4), 14491470. Planning Commission Report, 2003. National mission on biofuels. Published by Ministry of planning commission, Govt of India. Saka, S., Kusdiana, D., 2001. Biodiesel fuel from rapeseed oil as prepared in supercritical methanol. Fuel 80 (2), 225-231. Srivastava A, Prasad R. 2000. Triglycerides-based diesel fuel. Renewable and Sustainable Energy Reviews. Vol 4, 111-133. Toda, T., Honda, H., Fukumura, T., Sibasaki-Kitakawa, N., Yonemoto, T., 2004. Novel production method of biodiesel fuel using anion exchange resin as a heterogeneous catalyst. 10th Asian Pacific Confederation of Chemical Eng. Congress 2004, Kitakyushu, Japan. Warabi, Y., Kusdiana, D., Sakam, S., 2004. Reactivity of triglycerides and fatty acids of rapeseed oil in supercritical alcohols. Bioresource Technol. 91 (3), 283-287. Yamazaki, R., Iwamoto, S., Nabetani, H., Osakada, K., Miyawaki, O., Sagara, Y., 2004. Biodiesel fuel production by non-catalytic alcoholysis of oils. 10th Asian Pacific Confederation of Chemical Eng. Congress 2004, Kitakyushu, Japan.
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